JP2014127362A - Alkaline battery and method for manufacturing alkaline battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkaline battery excellent in discharge performance and liquid leakage resistance performance during overdischarge.SOLUTION: In an alkaline battery 1a, a plurality of positive electrode mixtures 3 (31-33) formed in an annular shape are inserted into a bottomed cylindrical metal-made battery can 2 serving also as a positive electrode. The positive electrode mixture contains electrolytic manganese dioxide as a positive electrode active material, the electrolytic manganese dioxide has a specific surface area measured by a BET method of 20 m/g or more 30 m/g or less, and the annular positive electrode mixtures are arranged to be laminated in a state where the positive electrode mixtures are separated from one another in a vertical direction coaxially with a cylindrical axis 10, when the extension direction of the cylindrical axis of the hollow cylindrical battery can is set to the vertical direction.

Description

  The present invention relates to an alkaline battery including a cyclic positive electrode mixture containing electrolytic manganese dioxide as a positive electrode active material.

  FIG. 1 shows a general structure of an alkaline battery which is an object of the present invention. The alkaline battery shown in the figure is an LR6 type cylindrical alkaline battery 1, and FIG. 1 shows a vertical sectional view of the alkaline battery 1 when the extending direction of the cylindrical shaft 10 is the vertical (vertical) direction. ing. The alkaline battery 1 includes a bottomed cylindrical metal battery can (positive electrode can) 2, a positive electrode mixture 3 formed in an annular shape, and a bottomed cylindrical shape disposed inside the positive electrode mixture 3. The separator 4, the negative electrode gel 5 containing zinc alloy and filled inside the separator 4, the negative electrode current collector 6 inserted into the negative electrode gel 5, and the electrolytic solution are housed as power generation elements. A negative electrode terminal plate 7 is fitted into the opening of the positive electrode can 2 via a sealing gasket 8 so that the storage space for the power generation element is sealed.

  The positive electrode mixture 3 is prepared by mixing electrolytic manganese dioxide (EMD) serving as a positive electrode active material, graphite serving as a conductive material, and an electrolytic solution together with a binder such as polyacrylic acid, and rolling, crushing, granulating, and classifying the mixture. After being processed in such a process, it is compressed and formed into an annular shape. A plurality of annular positive electrode mixtures 3 are press-fitted in the positive electrode can 2 so as to be coaxial with the cylindrical shaft 10 of the positive electrode can 2 while being stacked in the vertical direction in the positive electrode can 2. In the example shown in FIG. 1, three positive electrode mixtures 3 are stacked.

  And in order to improve the discharge performance of an alkaline battery by improving the positive electrode mixture side, the amount of the positive electrode mixture and the active material in the positive electrode mixture is increased, or the utilization efficiency of the positive electrode active material is improved. It is possible. Patent Document 1 below describes optimizing the specific surface area of EMD, which is a positive electrode active material, in order to improve the performance of an alkaline battery. Patent Document 2 below describes in detail a method for producing a positive electrode mixture, various physical properties of EMD including a specific surface area, and a method for measuring the physical properties.

JP-A-10-302793 JP-A-10-228899

  In order to improve the performance of the alkaline battery by improving the positive electrode mixture side, an increase in the amount of the positive electrode mixture and the positive electrode active material is expected to improve the discharge capacity. However, since it is necessary to increase the amount within the standard size of the battery, the proportion of the positive electrode active material in the positive electrode mixture is increased or the molding density of the positive electrode mixture is increased. However, when the blending ratio of the positive electrode active material is increased, the blending ratio of the conductive agent is decreased, the internal resistance is increased, and there is a problem that the high load discharge performance (large current discharge characteristics) is deteriorated. When increasing the molding density, the volume of the molded body is increased, the void volume inside the molded body is reduced, and the amount of liquid electrolyte impregnation is reduced, thereby reducing the utilization rate of the positive electrode active material, There arises a problem that the high-load discharge performance is deteriorated.

  Therefore, in order to increase the utilization rate of the positive electrode active material and increase the amount of the electrolyte to be impregnated into the positive electrode mixture molded body, if the fine void volume in the positive electrode mixture is increased, the molding is naturally performed. The density will be lowered. However, as the fine void volume is increased, the amount of the active material is reduced and the discharge capacity is reduced.

  Thus, it is difficult to dramatically improve the discharge performance of the alkaline battery by improving the positive electrode mixture side. Therefore, in the invention described in Patent Document 1, the specific surface area of the EMD is optimized from the viewpoint of increasing the utilization factor of the active material, but actually, the discharge performance is improved by improving the positive electrode mixture side. It is difficult to improve dramatically.

  On the other hand, the performance required for alkaline batteries is not limited to discharge performance. High safety is also required. For example, leakage resistance performance during overdischarge. And discharge performance and leak-proof performance are contradictory. In general, in order to improve the discharge performance, the positive electrode can is filled with a larger amount of a substance that causes a chemical reaction via the electrolytic solution. In other words, a sufficient amount of electrolyte solution is injected into the positive electrode can with respect to the amount of chemical reaction between the positive electrode active material and the negative electrode active material. However, at the time of overdischarge that discharges in a state where almost no chemical reaction occurs, the electrolyte solution is left in excess, and the excess electrolyte solution is decomposed, generating a gas that causes an increase in internal pressure and subsequent leakage. .

  Therefore, an object of the present invention is to provide an alkaline battery that has a discharge performance equal to or higher than that of a conventional alkaline battery and is excellent in leakage resistance.

The present invention for achieving the above object is an alkaline battery in which a plurality of positive electrode mixtures formed in an annular shape are inserted into a bottomed cylindrical metal battery can also serving as a positive electrode,
The positive electrode mixture includes electrolytic manganese dioxide as a positive electrode active material, and the electrolytic manganese dioxide has a specific surface area measured by a BET method of 20 m ² / g to 30 m ² / g,
With the extending direction of the cylindrical axis of the hollow cylindrical battery can as the vertical direction, the plurality of annular positive electrode mixtures are arranged in a stacked manner in a state of being spaced apart from each other in the vertical direction coaxially with the cylindrical axis.
The alkaline battery is characterized by this.

The present invention also extends to a manufacturing method of an alkaline battery in which a plurality of positive electrode mixtures formed in a ring shape are inserted into a bottomed cylindrical metal battery can also serving as a positive electrode. The invention concerned
Forming a positive electrode mixture containing manganese dioxide having a specific surface area of 20 m ² / g or more and 30 m ² / g or less as a positive electrode active material measured by the BET method in an annular shape;
A step of stacking and arranging the plurality of annularly formed positive electrode mixtures coaxially with the cylindrical shaft and spaced apart from each other in the vertical direction, with the extending direction of the cylindrical shaft of the hollow cylindrical battery can as the vertical direction ,
It is characterized by including.

  The alkaline battery according to the present invention has a discharge performance equal to or higher than that of the conventional battery and excellent leakage resistance.

It is a figure which shows the structure of a general cylindrical alkaline battery. It is a figure which shows the structure of the alkaline battery which is one Embodiment of this invention. It is a figure which shows the arrangement | positioning state of the positive mix in the positive electrode can which comprises the alkaline battery which concerns on the said embodiment.

=== Structure of alkaline battery ===
FIG. 2 is a diagram showing a schematic structure of an alkaline battery 1a according to an embodiment of the present invention. The individual elements (2 to 8) constituting the alkaline battery 1a are basically the same as those of the conventional alkaline battery 1 shown in FIG. However, in the alkaline battery 1a according to the present embodiment, a plurality of (here, three) positive electrode mixtures 3 stacked in the vertical direction in the positive electrode can 2 do not adhere to each other and have a gap D. It arrange | positions so that it may mutually space apart. Furthermore, the specific surface area of EMD which is a positive electrode active material constituting the positive electrode mixture 3 is optimized for the positive electrode mixture 3 that is spaced apart. Thereby, the alkaline battery 1a according to the present embodiment has a discharge performance equal to or higher than that of the conventional alkaline battery 1 and excellent leakage resistance.

=== Performance evaluation ===
Here, in order to evaluate the discharge performance and leakage resistance performance of the alkaline battery 1a according to the present embodiment shown in FIG. 2 and to define an appropriate numerical range of the specific surface area of the EMD in the positive electrode mixture, Various positive electrode mixtures having different conditions are prepared, and the positive electrode mixture is assembled into the positive electrode can 2 and the LR6 type alkaline battery 1 having the conventional structure shown in FIG. 1 and the present embodiment shown in FIG. An LR6 type alkaline battery 1a having a structure was prepared as a sample.

  In each sample, the positive electrode mixture 3 has an annular shape with an outer diameter of 13.5 mm and an inner diameter of 9.0 mm, and the size in the height direction is the mass of the positive electrode mixture 3 according to the sample, the EMD specific surface area, and the molding pressure. It is increased or decreased by. Further, the negative electrode gel 5 has a zinc concentration of 66%, and the mass thereof is increased or decreased so as to be proportional to the mass of the positive electrode mixture 3. The specific surface area of EMD is measured by the well-known BET method. Then, each sample was subjected to a discharge test and a leak test to evaluate discharge performance and leak resistance.

<About the arrangement of the positive electrode mixture>
As shown in FIG. 1 or FIG. 2, each sample is arranged such that the positive electrode mixture 3 stacked in the vertical direction according to the sample is in close contact with or separated from each other. FIG. 3 shows a state when a plurality of positive electrode mixtures 3 (31 to 33) are inserted into the positive electrode can 2 before sealing. Three positive electrode mixtures 3 (31 to 33) manufactured under the same conditions are inserted in one positive electrode can 2, and in the sample corresponding to the alkaline battery 1 having the conventional structure shown in FIG. Each positive electrode mixture 3 (31 to 33) is pressed in the same direction from the opening 22 of the positive electrode can 2 toward the bottom surface 21 and sequentially inserted into the positive electrode can 2 and is arranged in the vertical direction. The adjacent positive electrode mixtures (31-32, 32-33) are arranged in close contact with each other without being separated from each other. That is, the separation distance (D3, D4) between the positive electrode mixture (31-32, 32-33) in FIG.

  On the other hand, when the positive electrode mixture 3 (31 to 33) is arranged apart like the alkaline battery 1a shown in FIG. 2, the positive electrode mixture 33 that is first inserted into the positive electrode can 2 is the conventional alkaline battery. 1 is inserted with a constant pressure, and the lower surface 34 of the positive electrode mixture 33 is disposed in contact with the bottom surface 21 of the positive electrode can 2. For the positive electrode mixture (32, 31) to be inserted after the second one, as shown in FIG. 3, the upper surface (36, 35) of the positive electrode mixture (32, 31) from the opening end 22 of the positive electrode can 2 Until the distance (D2, D1) is measured. And by adjusting these distances (D1, D2) according to the height h of the positive electrode mixture 3 (31-33), the distance (D3) between each positive electrode mixture (31-32, 32-33) is adjusted. , D4) are provided apart from each other.

<Performance evaluation test>
Next, discharge performance and leakage resistance performance were evaluated for each of the produced samples. About discharge performance, the light load discharge test and the heavy load discharge test were done, and the discharge performance of both light load discharge performance and heavy load discharge performance was evaluated based on each discharge test result. The light load discharge test was performed by discharging for 4 hours a day with a load of 43Ω, and the light load discharge performance was evaluated according to the time (days) until the final voltage became 0.9V. In the heavy load discharge test, an electric capacity of 1500 mW was discharged in 2 seconds, and then a pulse discharge operation for 1 cycle in which the electric capacity of 650 mW was discharged in 28 seconds was performed 10 times in 1 hour, and the end voltage was 1.05 V. The heavy load discharge performance was evaluated according to the time (number of cycles) required. In addition, about each discharge performance of light load and heavy load, 5 individual | organism | solids were produced on the same conditions about each sample, and the discharge performance of each sample was evaluated by the average value of the 5 individual | organism | solid.

  On the other hand, the leakage resistance performance is evaluated based on the presence or absence of leakage after the leakage test, in which each sample is continuously discharged for 48 hours at a load of 10Ω and then stored at a temperature of 60 ° C. for 10 days. did. In the liquid leakage test, 10 individuals were used for each sample, and the leakage resistance performance of each sample was evaluated based on the proportion (%) of the individual individuals that leaked.

Table 1 shows the manufacturing conditions and evaluation results for each sample.

  Table 1 shows the manufacturing conditions of the positive electrode mixture 3 (31 to 33) in nine types of samples 1 to 9, the arrangement state in the positive electrode can 2, and the results of the discharge test and the liquid leakage test. In Table 1, Samples 1 and 2 have the same structure as the alkaline battery 1 according to the conventional example shown in FIG. 1, and Samples 3 to 9 are alkaline batteries according to this embodiment shown in FIG. It has the same structure as 1a. The discharge performance of each sample in Table 1 is a relative value when the performance of sample 1 is set as a reference (100%).

<About the arrangement and height of the positive electrode mixture>
In Samples 3 to 9, when three positive electrode mixtures 3 (31 to 33) were stacked on the samples 1 and 2 in which the three positive electrode mixtures 3 (31 to 33) were closely arranged in the vertical direction, The height of becomes higher. Therefore, the distance D1 from the opening end surface 22 of the positive electrode can 2 to the upper surface 35 of the uppermost positive electrode mixture 31 is naturally reduced. However, since the sealing body by the negative electrode terminal plate 7 and the sealing gasket 8 is fitted in the area near the opening end face 22 in the positive electrode can 2, there is a limit to the lower limit of the distance D1.

  Therefore, the amount of the positive electrode mixture 3 (31 to 33) is increased, and the distance D1 = 5.9 mm in the sample 2 having a high height h is equal to the height of D3 + D4 corresponding to the height of the gap D at two locations. In Samples 3 to 9, it was uniformly defined as D1 = 5.4 mm. Therefore, in Samples 3 to 9, the height h of the positive electrode mixture 3 (31 to 33) is positive of the sample 2 so that the positive electrode mixtures (31-32, 32-33) are reliably spaced from each other. The height is adjusted to be equal to or less than the height h of mixture 3 (31 to 33) = 14.3 mm.

  Further, in order to ensure that the three positive electrode mixtures 3 (31 to 33) in the positive electrode can 2 are spaced apart from each other, as described above, the positive electrode mixture 3 (31 to 33) An upper limit (h≈14.3 mm) is provided for the height h, and then the upper surface 36 of the second positive electrode mixture 32 disposed in the center in the vertical direction according to the height h of the positive electrode can 2. It is necessary to set the distance D2 to the opening end face 22 appropriately. Here, D2 = 10.2 mm in sample 2 was set to D2 = 19.8 mm in consideration of the gap D.

  Samples 5 to 9 were prepared for evaluating the relationship between the specific surface area of the EMD in the positive electrode mixture 3 (31 to 33) and the discharge performance and leakage resistance performance. 31 to 33), when pressed at the same pressure, the density is inversely proportional to the specific surface area of the EMD. Therefore, in the case of the annular positive electrode mixture 3 (31 to 33) having the same inner and outer diameters, the specific surface area of the EMD The greater the is, the higher the height h is. Therefore, the positive electrode mixture 3 (31 to 33) is pressed so that the height h of the positive electrode mixture 3 (31 to 33) in the sample 5 using the EMD having the largest specific surface area is substantially the same as that of the samples 2 and 4. The pressure at the time of molding was higher than those of Samples 1 to 4. Here, the press pressure is adjusted so that the height h of the positive electrode mixture 3 (31 to 33) in the sample 5 is h = 14.4 mm, and the samples 6 to 9 are also the positive electrode mixture 3 (31 in the sample 5). To 33) at the same press pressure as the positive electrode mixture 3 (31 to 33). For example, in the sample 6 in which the mass and the specific surface area of the positive electrode mixture 3 (31 to 33) are the same as those of the samples 2 and 4, the height h between the positive electrode mixture 3 (31 to 33) of the samples 2 and 4 is h = 14.3 mm. In contrast, in sample 6, h = 13.6 mm.

<Evaluation results>
As shown in Table 1, sample 2 with the same manufacturing conditions except that the positive electrode mixture 3 (31 to 33) is increased with respect to the reference sample 1 has both light and heavy load discharge performance. It was improved by about 10%. However, with respect to the leakage resistance performance, in Sample 1, half of the samples leaked after the leakage test were 50%, whereas in Sample 2, all the leaks occurred. It was confirmed that the performance and the leak-proof performance were contradictory.

  Samples 3 to 9 are samples in which the positive electrode mixture 3 (31 to 33) is spaced apart, and among these, the samples 3 and 4 are the positive electrode mixture 3 (31 to 33) with respect to the samples 1 and 2, respectively. Only the arrangement state of is changed. And in sample 3, although the performance was not improving with respect to sample 1 about light load discharge performance, about heavy load discharge performance, the sample 2 with which positive mix 3 (31-33) is increased and Equivalent performance was shown. Furthermore, the number of samples leaked by the leak test was 1 in 10 and it was confirmed that the leak-proof performance was significantly improved with respect to Samples 1 and 2. Further, in Sample 4 in which the positive electrode mixture 3 (31 to 33) is increased with respect to the sample 3 and the mass of the positive electrode mixture 3 (31 to 33) is set to 11.55 g as in the sample 2, the light load discharge performance Is equivalent to Sample 2, the heavy load discharge performance is further improved than Sample 2, and a 20% improvement in performance over Sample 1 was observed. And after the liquid leakage test, although it was inferior to the sample 3, with respect to the sample 2 with the same mass of the positive electrode mixture 3 (31-33), the number of occurrences of liquid leakage became 1/5. The number of individuals leaking from the reference sample 1 was also reduced by 30%.

Samples 5 to 9 are samples in which the specific surface area of the EMD was changed while the positive electrode mixture 3 (31 to 33) was spaced apart. The mass of the positive electrode mixture 3 (31 to 33) is 11.55 g which is the same as that of the samples 2 and 3. Here, when the evaluation result about the samples 5-9 shown in Table 1 is seen, about the light load discharge performance, like the sample 4, it depends on the mass of the positive electrode mixture 3 (31-33), and the sample 2 And the same performance as sample 4. About heavy load discharge performance, the tendency which improved, so that the specific surface area was large was seen. However, in Sample 5 having a specific surface area of greater than 30 m ² / g, the leakage resistance performance deteriorated, and the ratio of individuals in which leakage occurred due to the leakage test was 50%, which is the same result as Sample 1. Moreover, in the sample 9 whose specific surface area is smaller than 20 m < ² > / g, the heavy load discharge performance was falling rather than the sample 2 with the same mass of the positive electrode mixture 3 (31-33). Therefore, the optimum numerical range of the specific surface area can be defined as 20 m ² / g or more and 30 m ² / g or less.

=== Action, Effect ===
From the evaluation results shown above, in the alkaline battery according to this embodiment shown in FIG. 2, when the positive electrode mixture 3 (31 to 33) absorbs the electrolytic solution and swells, the positive electrode mixture 3 (31 -32, 32-33) has a space for absorbing the increase in volume due to the swelling, so that the positive electrode mixture 3 (31-33) can swell sufficiently, and as a result, the heavy load discharge performance is improved. Can be considered. That is, conventionally, the amount of electrolyte absorption was limited because there was no space commensurate with the volume increase associated with the absorption of the electrolyte of the positive electrode mixture 3 (31 to 33). 31-32, 32-33), since the gap D is provided, it can be considered that the electrolyte was absorbed more efficiently.

  However, if the specific surface area is too small, the EMD is inactive, that is, the surface area that contributes to the power generation reaction is reduced, and the effect of improving the heavy load discharge performance by disposing the positive electrode mixture 3 (31 to 33) is offset. I also found out. Further, when the positive electrode mixture 3 (31 to 33) is press-molded at the same pressure, the density decreases when the specific surface area of the contained EMD is large, and the density increases when the specific surface area is small. It was also found that when the surface area is too large, the filling efficiency of the positive electrode mixture 3 (31 to 33) is lowered, and the absorption efficiency of the electrolytic solution is lowered accordingly, and the leakage resistance performance is deteriorated. Therefore, in order to acquire the effect by arranging positive electrode mixture 3 (31-33) apart, it is necessary to adjust the specific surface area of EMD in positive electrode mixture 3 (31-33) appropriately. Become. In addition, the fact that the electrolytic solution is efficiently absorbed also means that the excess electrolytic solution is reduced, thereby improving the leakage resistance performance due to overdischarge.

  In Samples 3 to 9 in Table 1, since the distance D2 from the upper surface 36 of the positive electrode mixture 32 arranged in the center in the vertical direction to the open end surface 22 of the positive electrode can 2 was constant, the positive electrode mixture 3 (31 The distances (D3, D4) between the positive electrode mixtures (31-32, 32-33) corresponding to the height h of (33) to (33) were not uniform. However, as long as the performances of Samples 1 and 2 in which the positive electrode mixture (31-32, 32-33) are separated and Samples 3 to 9 shown in Table 1 are separated, As long as the performance test results in Samples 5 to 9 in which the specific surface area of the EMD was changed while separating the mixture (31-32, 32-33) were observed, the positive electrode mixture (31-32, 32-33) It is better to consider that there is no correlation between the distance (D3, D4) and the discharge performance or leakage resistance performance, or it is extremely small. That is, in the discharge performance and leakage resistance performance, the effect due to the difference in specific surface area of EMD is more dominant than the effect due to the difference in distance (D3, D4) between the positive electrode mixture (31-32, 32-33). It can be said that. In any case, since the height of the positive electrode can 2 is limited, the positive electrode mixture 3 (31 to 33) is stacked and disposed in the positive electrode can 2 in a state where the height restriction is satisfied and the positive electrode mixture 3 (31 to 33) is separated. In other words, if the specific surface area of the EMD is too large, the height h of the positive electrode mixture 3 (31 to 33) is increased, and eventually the gap D cannot be provided. Therefore, there is a great technical significance in defining the specific surface area of the EMD when the positive electrode mixture 3 (31 to 33) is spaced apart.

=== Other Embodiments ===
In the alkaline battery 1a according to the present embodiment, three positive electrode mixtures 3 (31 to 33) of the same size are inserted into the positive electrode can 2, but there are a plurality of positive electrode mixtures inserted into the positive electrode can. As long as the inner diameter and the outer shape of the ring are the same, a plurality of positive electrode mixtures having different heights may be mixed and inserted into one positive electrode can. In any case, the cylindrical axial direction method of the bottomed cylindrical positive electrode can may be the vertical direction, and a plurality of annular positive electrode mixtures may be inserted in a state separated in the vertical direction.

  Moreover, in the alkaline battery 1a which concerns on the said embodiment, although the positive mix 3 (31-33) was inserted in the positive electrode can 2 after being cyclically press-molded, as a shaping | molding method of a positive mix, As is well known, there is a method in which a powdered positive electrode mixture is filled in a positive electrode can, and then the positive electrode can itself is used as a press mold to press the powder to form an annular shape. Even when such a forming method is adopted, for example, a plurality of positive electrode mixtures are sequentially formed in a positive electrode can, and each time one positive electrode mixture is formed, a ring-shaped spacer corresponding to the gap D in FIG. A member may be inserted. The spacer member may be made of a material that does not inhibit swelling of the absorbed positive electrode mixture and has a certain degree of hardness during molding. It is conceivable that a material that absorbs and softens the electrolytic solution (liquid) or decomposes with the electrolytic solution, and after the decomposition, a material that does not hinder a chemical reaction in the battery or does not deteriorate the performance.

DESCRIPTION OF SYMBOLS 1,1a Alkaline battery, 2 positive electrode can, 3,31-33 positive electrode mixture, 4 separator, 5 negative electrode gel, 6 negative electrode current collector, 7 negative electrode terminal board, 8 gasket, 9 positive electrode terminal

Claims (2)

An alkaline battery in which a plurality of positive electrode mixtures formed in an annular shape is inserted into a bottomed cylindrical metal battery can also serving as a positive electrode,
The positive electrode mixture includes electrolytic manganese dioxide as a positive electrode active material, and the electrolytic manganese dioxide has a specific surface area measured by a BET method of 20 m ² / g to 30 m ² / g,
With the extending direction of the cylindrical axis of the hollow cylindrical battery can as the vertical direction, the plurality of annular positive electrode mixtures are arranged in a stacked manner in a state of being spaced apart from each other in the vertical direction coaxially with the cylindrical axis.
An alkaline battery characterized by that. A method for producing an alkaline battery in which a plurality of positive electrode mixtures formed in a ring shape are inserted into a cylindrical metal battery can with a bottom that also serves as a positive electrode,
Forming a positive electrode mixture containing manganese dioxide having a specific surface area of 20 m ² / g or more and 30 m ² / g or less as a positive electrode active material measured by the BET method in an annular shape;
A step of stacking and arranging the plurality of annularly formed positive electrode mixtures coaxially with the cylindrical shaft and spaced apart from each other in the vertical direction, with the extending direction of the cylindrical shaft of the hollow cylindrical battery can as the vertical direction ,
The manufacturing method of the alkaline battery characterized by including.

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